Steric effects enforce double stereoselective N-coordination in twelve-membered binuclear palladium(II)-complexes containing chiral bridging aminoalkyl-phosphine ligands

Zsófia Császár, Kristóf Stágel, Szabolcs Balogh, A. Bényei, G. Lendvay, Gergely Farkas, J. Bakos

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The configuration of the ligand's N-substituent was found to determine the stoichiometry and strict stereoselectivity of N-coordination in twelve-membered palladium dimers 2a-b. The novel palladium(II)-complexes 2a-b have been synthesized in the reaction of [Pd(COD)Cl2] and optically pure (S,S)-pentane-2,4-diyl based aminoalkyl-phosphine ligands Ph2PCH(CH3)CH2CH(CH3)NHR 1a-b (R = (R)-α-phenylethyl 1a, R = (R)-α-(1-naphthyl)ethyl 1b) with stereogenic nitrogen atom, and studied by various 1D and 2D NMR techniques in solution and in the case of 2a by single-crystal X-ray diffraction. As an unprecedented case, ligands 1a-b were found to yield exclusively 12-membered cyclic dinuclear Pd(II)-complexes with stereospecific coordination of both of the donor nitrogen atoms. Formation of the 12-membered ring is shown to reduce the steric hindrance of the bulky substituents with respect to the six-membered ring.

Original languageEnglish
Pages (from-to)59-62
Number of pages4
JournalJournal of Organometallic Chemistry
Volume855
DOIs
Publication statusPublished - Jan 15 2018

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phosphine
Palladium
phosphines
palladium
Ligands
nitrogen atoms
ligands
Nitrogen
Stereoselectivity
Atoms
crack opening displacement
rings
pentanes
X-Ray Diffraction
Stoichiometry
Dimers
stoichiometry
dimers
Nuclear magnetic resonance
Single crystals

Keywords

  • Aminoalkyl-phosphine
  • Binuclear complex
  • Palladium
  • Stereoselective coordination
  • Twelve-membered ring

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Steric effects enforce double stereoselective N-coordination in twelve-membered binuclear palladium(II)-complexes containing chiral bridging aminoalkyl-phosphine ligands. / Császár, Zsófia; Stágel, Kristóf; Balogh, Szabolcs; Bényei, A.; Lendvay, G.; Farkas, Gergely; Bakos, J.

In: Journal of Organometallic Chemistry, Vol. 855, 15.01.2018, p. 59-62.

Research output: Contribution to journalArticle

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AU - Balogh, Szabolcs

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AU - Lendvay, G.

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AB - The configuration of the ligand's N-substituent was found to determine the stoichiometry and strict stereoselectivity of N-coordination in twelve-membered palladium dimers 2a-b. The novel palladium(II)-complexes 2a-b have been synthesized in the reaction of [Pd(COD)Cl2] and optically pure (S,S)-pentane-2,4-diyl based aminoalkyl-phosphine ligands Ph2PCH(CH3)CH2CH(CH3)NHR 1a-b (R = (R)-α-phenylethyl 1a, R = (R)-α-(1-naphthyl)ethyl 1b) with stereogenic nitrogen atom, and studied by various 1D and 2D NMR techniques in solution and in the case of 2a by single-crystal X-ray diffraction. As an unprecedented case, ligands 1a-b were found to yield exclusively 12-membered cyclic dinuclear Pd(II)-complexes with stereospecific coordination of both of the donor nitrogen atoms. Formation of the 12-membered ring is shown to reduce the steric hindrance of the bulky substituents with respect to the six-membered ring.

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